Preparation of new and novel and useful electro-conductive polymer compositions is herein described. These compositions are produced by the dispersion of electrically conductive particulates in polymer vehicles. The conductivity of said dispersions as well as their ease of preparation, fabrication, and in many instances the resulting product's physical properties are shown to be substantially improved via the introduction of minor proportions of certain new and novel organo aluminates, titanates and/or zirconates of this invention. Additionally shown to be useful in production of comparably improved compositions are certain heretofore described organotitanates.
A proposed explanation of the mechanism of utility of these additives together with data describing the preparation of preferred embodiments of the aluminates, titanates and zirconates useful in the practice of this invention are hereinafter provided.
It has long been known to those skilled in the art that the dispersion of conductive particulates in polymeric media provides a means for the production of conductive compositions which enjoy varying proportions of the advantages of formability, corrosion protection and ease of application associated with the polymer matrix. Unfortunately, such compositions usually lose a very substantial proportion of the conductivity of the particulate being dispersed, and furthermore present substantial difficulties in preparation, fabrication and stabilization prior to usage. It has now been shown that certain aluminates, titanates and zirconates are the instant invention as well as certain analogous organotitanates heretofore described. When employed singly or in combination at levels based on conductor content of from 0.001 to about 5%, preferably from about 0.1% to about 1%, said additives will substantially enhance conductivity, the ease of manufacture and both stability and formability of the resulting dispersions.
The generic structure of the additives useful in the instant invention is shown in structures I and II. ##STR1## wherein, M is chosen from among aluminum, titanium and zirconium, a and b are independently 0, 1 or 2 within the constraint that a+b must equal 1 or 2; c, d and e are independently each 0, 1, 2 or 3 within the constraint that c+d+e must equal 3-(a+b) when M is aluminum or 4-(a+b) when M is either titanium or zirconium; f is 0 or 1, g is 1, 2 or 3 within the constraint that f+g must equal 2 or 3, h and j are independently each 0, 1 or 2 within the constraint that j+h must equal 1 when M is aluminum or 2 when M is either titanium or zirconium. R and R.sup.1 are each independently chosen from among monovalent 1 to 12 carbon alkyl groups, 2 to 12 carbon alkenyl groups, and 7 to 12 carbon aralkyl groups. Each of the aforegoing choices for R and R.sup.1 may optionally contain up to 2 carbon bound halogen atoms and/or up to 3 ether linked oxygen atoms. R.sup.2 and R.sup.3 are each independently either hydrogen or chosen from among the same groups as given above for R and R.sup.1. C, D, E and J are monovalent ligands each independently chosen from among monovalent mono, di, or tri amine substituted; alkanols having from 1 to 18 carbon atoms, aryl alcohols having from 6 to 12 carbon atoms each or alkenols having from 2 to 18 carbon atoms each. Each of the above groups may optionally contain up to 2 saturated (1 to 8 carbon) or unsaturated (1 to 8 carbon) carboxamide and/or up to 3 aromatic chlorine or bromine substituents and/or up to 3 ether oxygen atoms. Alternatively, C, D, E, H and J may be independently chosen from among di and tri ester pyrophosphates having the generic formulae: EQU --OP(O)(OR.sup.5)OP(OR.sup.6)(OR.sup.7)(O) III.
wherein, R.sup.5, R.sup.6 and R.sup.7 are all monovalent groups either all independently chosen from among: alkyl groups having from 1 to 18 carbon atoms each, alkenyl groups having from 2 to 18 carbon atoms each, aryl and aralkyl groups having from 7 to 12 carbon atoms each. R.sup.5, R.sup.6 and/or R.sup.7 may each contain up to 2 aromatic bound chlorine or bromine substituents or up to 4 ether bound oxygen atoms; or two members of the set R.sup.5, R.sup.6, R.sup.7 may be chosen as indicated above and the third may be chosen from among: hydrogen, an amine having the formula IV or a phosphate having the formula V. EQU NR.sup.8, R.sup.9, R.sup.10, R.sup.11 IV. EQU HP(OR.sup.12)(OR.sup.13)(OR.sup.14) V.
wherein, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are each monovalent groups chosen from among hydrogen, or the same groups as given for R and R.sup.1, alternatively two or more of the groups R.sup.8, R.sup.9, R.sup.10 and/or R.sup.11 may join to form a divalent or trivalent group attached to nitrogen in such a manner as to form ring structures (e.g., N-methyl, N-phenylmorpholinium). Alternatively, R.sup.8, R.sup.9 and R.sup.10 may be chosen as indicated above and R.sup.11 chosen from among 1 to 6 carbon alkyl, 6 to 12 carbon and aralkyl or alkenyl groups having 1 or 2 acrylato, acrylamido, methacrylato or methacrylamido substituents, or any combination thereof totaling either 1 or 2 substituents or up to 2 carbon bound hydroxyl groups. R.sup.12 may be chosen from the same groups as for R.sup.8 and R.sup.13 and R.sup.14 may be each independently chosen from the same groups as for R.sup.8 except for hydrogen. Ring structures produced via joining two or more of the ligands R.sup.12, R.sup.13, R.sup.14 may also be employed, e.g., ##STR2##
All of the organoaluminates and zirconates embodied in formulae I and II are new and novel compounds as are those organotitanates embodied in said formulae wherein R.sup.5 is other than H, an amine salt, or a protonated diallyl phosphite.
Preferred embodiment of the instant invention are those in which R and R.sup.1 contain from 1 to 6 carbon atoms each and wherein R.sup.2 and R.sup.3 are each chosen from any hydrogen methyl or ethyl groups. Preferred methods for the introduction of the aluminate, titanate and/or zirconate additive is dependent, in a large part, upon the nature of the polymer vehicle being employed, particularly its melting point and the processing temperatures to be utilized. In most applications wherein the thermal decomposition temperature of the additive(s) is exceeded prior to liquification of the vehicle, it is necessary to mechanically preblend the additive(s) with the conductive particulate is such a fashion as to obtain a thoroughly coated particulate, preferred coating levels do not exceed 5 additive molecules in depth and most preferred are those in which the additive coating level is 1 molecular thickness of additive, i.e., 0.01 to 5 wt.% on particulate, preferably 0.1 to 1.0 wt.% on particulate depending upon functional surface area. Such coatings may be achieved via the simple expedient of mechanically blending by providing adequate time and shear of the additive(s) with the conductive particulate at temperatures in the range of approximately -60.degree. to approximately 200.degree.-500.degree. C. with the upper limit being determined by the thermal decomposition temperature of the additives. If desired, a compatibilizing fluid such as inert vehicle, e.g., hydrocarbon solvent, alkanol, ester, ether, or in some instances water, may be employed to improve contact potential of the additives with the particulate. Subsequently, the vehicle, if employed, may be removed by techniques well known to the art or in the case of formulations in which the vehicle is a tolerable diluent left in place on the coated particulate. Equipment suitable for such mechanical preblending includes, but is not limited to high shear mixers such as Henschels, moderate shear mixing equipment such as a Patterson-Kelly, cone blenders, and over prolonged periods, lower specific energy equipment such as ribbon blenders. The techniques employed in preblending the additives of the instant invention with the conductive particulates are not critical to the utility of the products of this invention. All that is critical is that the coating applied be thin and uniform and that the major portion of the surface of the conductor be largly covered with additive(s). Once the additive has been applied to the conductive particulate, either through in situ methodology or via preblending, the thermal stability of the treated composite additive/conductive particulate is substantially increased, therefore, stabilizing the composite product sufficiently to permit processing by conventional techniques at temperatures to and, in many instances, in excess of 650.degree. C. (in inert atmospheres). As a practical matter, the in situ technique is most readily employed in those polymer vehicles which are adequately mobile for processing at temperatures below approximately 300.degree. C. and the preblend technique is generally preferred for applications in higher temperature process systems. Examples of the new and novel additives of the instant invention are given in Table 1 and examples of those previously described organotitanates which are useful in the practice of the instant invention are given in Table 1b.
TABLE 1 __________________________________________________________________________ K, CH.sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OAl(OC.sub.6 H.sub.4 NHCHCH.sub.2).sub.2 L, (CH.sub.3).sub.3 COAl(OC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NH.sub.2)(OC.s ub.2 H.sub.4 OC.sub.2 H.sub.4 NHCH.sub.3) M, ((C.sub.2 H.sub.5 OC.sub.2 H.sub.4).sub.2 CHO).sub.2 AlOC.sub.6 H.sub.3 Br.sub.2 NHCH(CH.sub.3).sub.2 CH.sub.3 N, (CH.sub.3).sub.2 CHOAlO(CH.sub.2).sub.6 N(CH.sub.3).sub.2 (OCH.sub.3) O, CH.sub.2CHCH.sub.2 OAlOP(O)(OH)OP(O)(OCH.sub.3)(OC.sub.4 H.sub.7) OP(O)(OC.sub.6 H.sub.11)OP(OCHCH.sub.2)(OC.sub.6 H.sub.4 C.sub.2 H.sub.5) P, C.sub.5 H.sub.9 OAlOP(O)((ONH(C.sub.2 H.sub.4 OCOCHCH.sub.2)(CH.sub.3). sub.2))OP(O)(OC.sub.8 H.sub.7)(OC.sub.4 H.sub.9).sub.2 Q, ##STR3## R, ##STR4## S, (C.sub.5 H.sub.9 O)(C.sub.2 H.sub.5 O)Ti((OP(O)(OC.sub.6 H.sub.4 Cl))P(O)(OCHCH.sub.2).sub.2)).sub.2 T, (OCH.sub.2 CH(CH.sub.3)CH.sub.2 O)TiOP(O)(OCH.sub.2 C.sub.6 H.sub.4 CH.sub.3)OP(O)(OCH.sub.3)((OCH(C.sub.6 H.sub.5).sub.2)) OP(OH)(O)OP(O)(OC.sub.2 H.sub.5).sub.2 U, (CH.sub.3 O)(CH.sub.3 OCHCH.sub.2 O)ZrOCH.sub.2 N(CH.sub.3)(C.sub.6 H.sub.11).sub.2 V, (n-C.sub.9 H.sub.19 O)Zr((O(CH.sub.2).sub.4 NH.sub.2))(OC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NH.sub.2).sub.2 X, (OC(O)(CH.sub.2).sub.2 O)ZrOP(O)(OCH.sub.3)OP(O)((ON(C.sub.2 H.sub.4).s ub.3 (CH.sub.3)) Y, (C.sub.6 H.sub.5 CH.sub.2 O).sub.2 Zr((OP(O)(OH)OP(O)(OC.sub.4 H.sub.9).sub.2)).sub.2 Z, (CH.sub.3 O)ZrOP(O)((OHP(OH)(OCH.sub.3).sub.2))OP(O)(OCH.sub.3)(OC.sub. 5 H.sub.11) ((OP(O)(OCH.sub.3)OP(O)(OC.sub.5 H.sub.11)((OHP(OCH.sub.3).sub.3)) ((OP(O)(OC.sub.5 H.sub.11)OP(O)(OCH.sub.3)((OHP(OCH.sub.3).sub.3)) AA, C.sub.2 H.sub.5 OZr(OC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NH.sub.2 ).sub.3 AB, ((CH.sub.3).sub.2 CHO)).sub.2 ZrOP(O)(OH)OP(O)(OC.sub.2 H.sub.5)OC.sub. 4 H.sub.9) OP(O)(ONH.sub.3 CH.sub.2 OH)OP(OC.sub.2 H.sub.5)(OC.sub.4 H.sub.9) AC, CH.sub.3)ZrOP(O)((ONH(C.sub.2 H.sub.4 OH).sub.3)(OP(O)(OC.sub.8 H.sub.17).sub.2 AD, (CH.sub.3).sub.2 CHO.sub.2 Ti(OP(O)(OC.sub.3 H.sub.17)OP(O)(OC.sub.8 H.sub.17).sub.2 __________________________________________________________________________
TABLE 1b __________________________________________________________________________ BA, (CH.sub.3).sub.2 CHOTi(OC.sub.2 H.sub.4 NHC.sub.2 H.sub.4 NH.sub.2).sub .3 BB, (OCH.sub.2).sub.2 Ti((OP(O)(OH)OP(O)(OC.sub.8 H.sub.17).sub.2)).sub.2 BC, (CH.sub.3).sub.2 CHOTiOP(O)((OHP(OH(OC.sub.8 H.sub.17).sub.2))(OP(O)(OC H.sub.3)(OC.sub.4 H.sub.9).sub.3 BD, ((CH.sub.3).sub.2 CHO)).sub.2 Ti((OC.sub.2 H.sub.4 N(C.sub.2 H.sub.4 OH).sub.2)).sub.2 __________________________________________________________________________
It should be noted that the examples provided in the above mentioned tables are intended to be illustrative rather than exhaustive of the molecular variations of organo aluminates, titanates and zirconates heretofore described generically which have been found useful in the production of highly electroconductive polymeric composites and that many other analogous variations and combination of the various component ligands and/or additives will be obvious to those skilled in the art.
Examples 1 and 2 are illustrative of techniques which may be employed to produce the additives of the instant invention and examples 3 through 7 are illustrative of processes whereby the use of the above mentioned additives may be beneficially applied to the surface of conductive particulates in order to produce composite materials suitable for incorporation into the highly conductive polymeric composites of the instant invention. Neither the process information with respect to additive preparation nor that associated with the application of said additives to conductive particulates and/or composites is intended to be exhaustive. Those skilled in the art will easily observe that substantially unlimited variations of well known organic chemical and mechanical technology respectively may be employed to produce the indicated additives and/or treated conductive particulates and/or composites respectively. It should be noted that the utility of the additives of this invention, for the purpose indicated, is surprising since the additives themselves are very poorly conductive and as such, one would expect that a surface layer of said additive on a relatively highly conductive material would degrade rather than improve the latter's conductivity contribution in a dispersion. Examples 8 through 20 are illustrative of the production of highly conductive composites by the incorporation of organometallic additives of the type heretofore described and a conductive particulate in a polymeric matrix. In many instances, it is not necessary to isolate the organometallic additive useful in the practice of this invention in the pure form in that such materials produced as a component of a mixture have been employed directly with excellent effect. Specific illustration of the last are given in examples 8 through 14, whereas examples of the pretreatment of particulate technique and usage of pretreated particulates are given in Examples 15, 16, 17 and 18, and the examples of in situ application of prepurified additive are given in Examples 19 through 24, respectively. Those skilled in the art will be fully cognizant of the fact that the examples given may be essentially reproduced in terms of their utility via obvious modification and/or alternative technology well known to those skilled in the art without departing from the essential novelty and utility associated with the products of the instant invention which comprise the new and novel aluminates, titanates and zirconates and the fully described heretofore, composites produced by the application of the aforesaid additives and other organotitanates previously described to produce conductive particulates and ternary products employing said organometallic additives in conjunction with conductive particulates and polymer or resin substrates or binders or particulate conductive materials pretreated with the above mentioned organometallics utilized in conjunction with polymeric substrates resins or binders in order to produce highly conductive polymeric composites.
Further objects of this invention and substantial substantiation of their novelty and utility will become apparent to the reader upon studying the examples hereinafter provided.